Benzene derivatives containing halogenated methyl groups and process of preparing them



Patented June 21, 1938 UNITED STATES PATENT OFFICE BENzENE DERIVATIVES CONTAINING HAL- OGENATED METHYL GROUPS AND PROC- ESS oF PREPARING THEM Otto Scherer, Willy Schumacher, and Fritz Miiller, Frankfort-on-the-Main, Germany, as-

signors to General Aniline Works, Inc., New

York, N. Y., a corporation of Delaware N Drawing. Application October 20, 1936, Se-

;rial No. 106,694. 1935 7 Claims.

The present invention relates to benzene derivatives containing halogenated methyl groups and to a process of preparing them, more particularly it relates to compounds "corresponding with the following general formula:

CFa

wherein X stands for hydrogen, chlorine or fluorine, Y1 and Y2 stand for hydrogen, halogen or the trifluoromethyl group and Y3 stands for hydrogen or halogen.

In the exhaustive side-chain chlorination of benzene derivatives containing in the nucleus more than one methyl group, such as, for instance,

meta-xylene or para-xylene, mesitylene or a substitution product or derivative thereof, for instance, according to the process of French Patent 798,727, it is easily possible to exchange all the hydrogen atoms in the side-chains for chlorine with formation of metaor para-xylenehexachloride, mesitylene-nonachloride and soon. By using, however, in this reaction benzene deriva- V tives which contain two methyl groups in orthoposition to one another as, .for instance, orthoxylene or pseudocumene, the absorption of chlorine is finished when all three hydrogen atoms of the one methyl group andtwo hydrogen atoms of the other methyl group in ortho-position have been exchanged for chlorine; it is not possible to exchange for chlorine the remaining hydrogen atom of the second methyl group in ortho-position and to obtain, for instance, the ortho-xylenehexachloride 0r pseudo cumene nonachloride.

Consequently, there cannot be made, according to this method, derivatives of orthoxylene, or substitution products thereof, which are entirely halogenated in the side chains.

We have found that benzene derivatives containing two trihalogenmethyl groups in orthoposition are obtainable by first pentachlorinating the two methyl groups, in ortho-position, of ortho-dimethylbenzenes and exchanging then the chlorine for fluorine by oneof the known methods,

for instance by the process of German Patent %575593. Thereby an ortho trifluoromethyl-ben- In Germany October 25,

zalfluoride of the following formula is obtained:-

wherein X stands for hydrogen or a substituent.

It is surprising that in this compound the remaining hydrogen atom of the side chain can be exchanged for chlorine so that a benzene derivative entirely halogenated in both methyl groups in ortho-position and corresponding with the following formula:

GFa

terials, for instance, for the manufacture of dye-- stuffs or fungicides and/or insecticides.

The following examples serve to illustrate the invention, but they are not intended to limit it thereto. l

(1) Ortho-xylene is chlorinated, for instance by the process of French Patent 798,727. After absorption of 5 chlorine atoms, the chlorination is at an end. The ortho-xylene-penta-chloride is obtained in i a nearly quantitativeyield; it, forms a white crystalline mass melting at 48,

C. It is treated, for instance, according to the statements 'of German Patent 575,593, with anhydrous hydrogen fluoride, whereby the orthoxylenepentafiuoride is obtained, The latter forms a liquid which is clear *asrwater and boils at 140-142 'C. under ordinary pressure.

is i The ortho-xylenepentafluoride is further chlorinated and there is obtained with a very good yield the l-trifluoromethyl-2-difluorochloromethylbenzene which forms a liquid clear as water and boils at l68-1'70 C. underordinary pressure.

In the compound thus formed the chlorine may be exchanged for fluorine with formation of orthoxylenehexafluoride which forms a colorless liquid boiling at 140-142 C. under ordinary pressure.

In a quite similar manner there may be obtained from 4-chloro-ortho-xylene by way of 4-chloro-1-trichloromethyl-2-benzalchloride and -chloro-1-trifluoromethyl-2-benzalfluoride (colorless liquid boiling at 164=-16'7 C. under ordinary pressure) the 4-chloro-l-trifluoromethyl- 2-difluorochloromethylbenzene (colorless liquid boiling at '7477 C. under a pressure of 18 mm.) and the 4-chloro-l.2-xylenehexafluoride which is a colorless liquid boiling at 160-16 1 C. under ordinary pressure. From dichloro-ortho-xylene there are obtained the corresponding compounds which are twice chlorinated in the nucleus.

(2) In the manner described in Example 1 there is obtained from pseudocumene first the pseudocumene-octachloride, probably of the formula:

GOls

CHCh

a white crystalline body melting at 70 C., and from this product the pseudocumene-octafluoride, probably of the formula:

l CF:

which forms a colorless liquid boiling under ordinary pressure at Mil-143 C. By chlorinat- C ClF:

forming a colorless liquid boiling under ordinary pressure'at ISO-163 C. By exchanging in the latter compound chlorine for fluorine the pseudoclunene-nonafluoride, probably of the formula:

I CF:

is obtained, forming a colorless liquid boiling at 140-143 C. under ordinary pressure.

In quite a similar manner there are obtained from chloroand di-chloro-pseudocumene the corresponding products which are halogenated in I the nucleus. From durene there is obtained by way of durene-decachloride the durene-decafluoride, from this body the bis-trifluoromethylbis-difluorochloromethylbenzene and from the latter the durene-dodecafluoride.

We claim:

1. The process which comprises pentachlorinating the two methyl groups, in ortho-position, of ortho-dimethylbenzenes, exchanging then the chlorine for fluorine and replacing the remaining hydrogen atom of the side chain by chlorine.

2. The process which comprises pentachlorlnating the two methyl groups, in ortho-position, of ortho-dimethylbenzenes, exchanging then the chlorine for fluorine, replacing the remaining hydrogen atom of the side chain by chlorine and exchanging in the ortho-trifluoromethyl-difluoro-chloromethylbenzenes thus obtained the chlorine in the side chain for fluorine.

3. The compounds of the following general OXF where X is one of the group consisting of hydrogen, chlorine and fluorine, Y is one of the group consisting of hydrogen, chlorine and CXFz and Z is one of the group consisting of hydrogen, chlorine and CFa.

4- The compounds of the following general formula:

CF: OCR, Y

where Y and Z stand for members of the group consisting of hydrogen, chlorine and CF3.

5. The compound of the following formula:

being a colorless liquid which bolls at 140-142 C. under ordinary pressure.

6. The compound of the following formula:

being a colorless liquid which boils at ISO-164 C. under ordinary pressure.

'7. The compound of the following formula:

7 formula:

being a colorless liquid which boils at BIO-143 C. under ordinary pressure.

OTTO SCHERER.

WILLY SCHUMACI-IER.

mrrz MULLER. 

